{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,15]],"date-time":"2026-10-15T15:55:58Z","timestamp":1792079758730,"version":"4.4.0"},"reference-count":80,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2025,12,10]],"date-time":"2025-12-10T00:00:00Z","timestamp":1765324800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"},{"start":{"date-parts":[[2025,12,10]],"date-time":"2025-12-10T00:00:00Z","timestamp":1765324800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/100031478","name":"NextGenerationEU","doi-asserted-by":"publisher","award":["NPOO.C3.2.R2\u2010I1.06.0041"],"award-info":[{"award-number":["NPOO.C3.2.R2\u2010I1.06.0041"]}],"id":[{"id":"10.13039\/100031478","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["febs.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["FEBS Open Bio"],"published-print":{"date-parts":[[2026,4]]},"abstract":"<jats:p>\n                    Plastic waste from fossil\u2010derived polymers remains a major environmental challenge, driving interest in biopolymers and enzyme\u2010enabled end\u2010of\u2010life strategies. This review synthesizes current understanding of how polymer structure and thermal state govern enzymatic degradability, with emphasis on semicrystalline architectures and state\u2010dependent accessibility. Within the Keller\u2013Flory two\u2010phase framework, crystalline lamellae embedded in an amorphous matrix dictate water\/enzyme diffusion, chain mobility, and hydrolysis kinetics. Enzymatic attack preferentially initiates in amorphous regions, producing characteristic biphasic behavior as amorphous domains erode faster than crystalline regions, leading to crystallinity enrichment and subsequent slowing of degradation. Thermal transitions further modulate this balance: near or above\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>g<\/jats:sub>\n                    , segmental mobility and free volume rise, accelerating hydrolysis if enzymes remain stable; above\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    , chain mobility is maximal, but enzyme stability typically limits feasibility. Processing and architecture also strongly influence outcomes: annealing increases crystallinity and slows mass loss, quenching suppresses crystallization and hastens degradation, random copolymerization disrupts packing and lowers\n                    <jats:italic>T<\/jats:italic>\n                    <jats:sub>m<\/jats:sub>\n                    , while block copolymers often degrade selectively by domain. Recent advances expand the operational window toward rubbery or near\u2010molten states for low\u2010melting aliphatic polyesters (e.g., PCL, PLGA, PEG\u2010\n                    <jats:italic>b<\/jats:italic>\n                    \u2010PLA), leveraging thermophilic\/engineered hydrolases (cutinases, PETases, lipases, carboxylesterases) with demonstrated stability at 60\u201390\u2009\u00b0C. Emerging strategies\u2014including enzyme thermostabilization, AI\u2010guided design, disulfide grafting, smart encapsulation, and\n                    <jats:italic>in\u2010situ<\/jats:italic>\n                    enzyme embedding\u2014enable self\u2010degradation of materials and accelerate inside\u2010out depolymerization under mild triggers. Integrating thermal analysis with polymer morphology and enzyme engineering offers a path to programmable, circular end\u2010of\u2010life for biopolymers, translating fundamental structure\u2013property\u2013reactivity relationships into practical enzymatic recycling and reduced environmental impact.\n                  <\/jats:p>","DOI":"10.1002\/2211-5463.70177","type":"journal-article","created":{"date-parts":[[2025,12,10]],"date-time":"2025-12-10T09:45:21Z","timestamp":1765359921000},"page":"670-685","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":12,"title":["Enzymatic degradation of biopolymers in amorphous and molten states: mechanisms and applications"],"prefix":"10.1002","volume":"16","author":[{"given":"An\u0111ela","family":"Pustak","sequence":"first","affiliation":[{"name":"Radiation Chemistry and Dosimetry Laboratory, Division of Materials Chemistry Ru\u0111er Bo\u0161kovi\u0107 Institute  Zagreb 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